Aminecarbotrithioates and preparation

ABSTRACT

A THIOLSULFONATE IS REACTED WITH AN AMINECARBODITHIOATE SALT TO GIVE AN AMINECARBOTRITHIOATE PRODUCT. THE PRODUCTS OF THIS INVENTION HAVE BIOLOGICAL ACTIVITY. PARTICULARLY IN CONTROLLING MICROORGANISMS AND OTHER PESTS.

United States Patent AMINECARBOTRITHIOATES AND PREPARATION Joseph E.Dunbar and Joan H. Rogers, Midland, Mich.,

awslsiighnors to The Dow Chemical Company, Midland,

No Drawing. Continuation-impart of abandoned application Ser. No.682,511, Nov. 13, 1967. This application July 26, 1971, Ser. No. 166,258a Int. Cl. C0711 87/46 US. Cl. 260-246 B ABSTRACT OF THE DISCLOSURE Athiolsulfonate is reacted with an aminecarbodithioate salt to give anaminecarbotrithioate product. The products of this invention havebiological activity, particularly in controlling microorganisms andother pests.

This application is a continuation-in-part of US. patent applicationSer. No. 682,511, filed Nov. 13, 1967, now abandoned.

BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION The process of thisinvention is represented by the following equation:

masons. i'lfiNRrRr mssoumm 1:16am

s ii iii (A) and wherein R R R and R are defined below, to give themonoand bis-aminocarbotrithioate products hereinafter shown.

The process of this invention gives rise to the following products,indicated by Formulas I-VI, as represented by the following equation:

mesons. zitonatn. mssc mniat itsn,

' wherein R represents alkenyl, loweralkylor halo-substituted alkenyl,2-(loweralkoxy)ethyl, 2-(aryloxy)ethyl or propargyl, R representsloweralkyl, aryl or loweralkyl or halo-substituted aryl and wherein Rand R individually represent lower alkyl or hydrogen and togetherrepresent the remaining portion of a heterocyclic ring containing thenitrogen atom;

RIRINfiSB(CHI)nSS(IfNR RQ 3 I) wherein n represents an integer from 1,to 2, to 3, to 4,

3,810,890- Patented May 14, 1974 to 5, to 6, to 7, to 8, to 9, to 10, to11, to 12, and wherein R; and R individually represent loweralkyl orhydrogen and together represent the remaining portion of a hetero cyclicring containing the nitrogen atom;

S I) nSSJ'iNR-iRg (CH!) nSSCNRIR (III) wherein R and R individuallyrepresent lower alkyl or hydrogen and together represent the remainingportion of a heterocyclic ring containing the nitrogen atom; wherein nrepresents 0 or 1; wherein each Z may be the same or different andrepresents loweralkyl, hydrogen, chloro, bromo, iodo, loweralkoxyl,nitro or loweralkylthio; and wherein m is 1, to 2, to 3 to 4-, not morethan two Z, groups of which are iodo or nitro;

wherein R and R individually represent loweralkyl or hydrogen andtogether represent the remaining portion of a heterocyclic ringcontaining the nitrogen atom; R represents lower alkyl, phenyl,loweralkylphenyl, halophenyl or lower alkoxyphenyl; n is 1, to 2 and Xis O or cmwmnsscrsmm wherein R and R individually represent loweralkylor hydrogen and together represent the remaining portion of aheterocyclic ring containing the nitrogen atom; and wherein n is 10, to11, to 12, to 13, to 14, to 15, to 16, to 17, to 18, to 19, to 20;

R R;NCsSCHaCH:-S-CHzCHr-SSCNRsIh wherein R and R individually representloweralkyl or hydrogen and together represent the remaining portion of aheterocyclic ring containing the nitrogen atom.

As used in the specification and claims, the terms loweralkyl andloweralkoxy" designate alkyl and alkoxy groups having from 1 to 4 carbonatoms, such as, for example, methyl, ethyl, propyl and butyl; andmethoxy, ethoxy, propoxy and butoxy, respectively.

DETAILED DESCRIPTION OF THE INVENTION The process of this invention canbe represented by the following equation for themonoaminecarbotrithioatc Formula I compounds, the reaction involvedbeing equally operable in the preparation of Formula II-VI compounds:

mssom, iro narm -s nlssonara. rirdsa.

ii (I wherein:

M+=alkali metal or ammonium cation R,=loweralkyl, aryl or substitutedaryl 'R, =alkenyl, substituted alkenyl, 2-(loweralkylthio) ethyl,

2-(arylthio)ethyl, 2 (loweralkoxy)ethyl, 2-(aryloxy) ethyl or propargyland wherein R and R represent the remaining portion of a heterocyclicring containing the nitrogen atom.

chloride, chloroform, ethyl ether, benzene, toluene, xylene orcommercial chlorinated solvents, and the carbo'di: thioate salt may bedissolved in water. The two solutions are then mixed and vigorouslyagitated for a period of time from minutes to 20 hours advantageously ata temperature ranging between 20 and 150 C. Again, both reactants may becompletely soluble in a single organic solvent, or only one reactant maybe completely soluble in the single organic liquid or neither reactantmay be completely soluble in the single organic liquid. For anotherexample, a solution of the thiolsulfonate in ethanol can be added to asuspension of the carbodithioate salt in ethanol, and the resultingmixture stirred at the required temperature to cause reaction. Solventsuseful in single organic liquid systems include ethanol, methanol,

isopropanol, acetone, methylethyl-ketone, methylene chlo' v ride,chloroform, benzene, toluene, or xylene. When op crating above theboiling point of the solvent system, a pressure vessel is advantageouslyused.

The amounts of the reactants to be employed in the reaction are notcritical, some of the desired products being obtained when the reactantsare employed in any proportions. In a preferred method, good yields are'obtained when employing substantially stoichiometric pro portions ofthe reactants. Bis(aminecarbotrithioates) are advantageously prepared byreacting two equivalents of an amlinecarbodithioate, for example, sodium4-min-v pholinecarbodithioate, with one equivalent of a thiosulfonate,for example, 2,2'-bis(phenylsulfonylthio)diethyl sulfide to givethiodiethylene bis(morpholinecarbotrithioate). Up to 100 percent excessof either reactant is not deleterious, however.

Representative thiolsulfonates useful in the process 0 this inventioninclude o-nitrophenyl benzenethiolsulfonate, dinitrophenylbenzenethiolsulfonate, 2,3,3-tribromoallyl p-toluenethiolsulfonate,2,3,3-tribromoallyl benzenethiolsulfonate, p-phenylene bis(methanethiosulfonate) pentamethylene bis (methanethiolsulfonate), allylp-toluenethiolsulfonate,

cc,cc'-biS (methyl sulfonylthio) -o-xylene, propargylp-toluenethiolsulfonate,

methyl methanethiolsulfonate, 2-methylbenzyl benzenethiolsulfonate,

ethyl p-toluenethiolsulfonate,

n-dodecyl p-toluenethiolsulfonate,

benzyl p-toluenethiolsulfonate, 2-(methy1thio)ethylp-iodobenzenethiolsulfonate, 2-(methylthio)ethyl methanethiolsulfonate,2,2'-bis(phenylsulfonylthio)diethyl sulfide, 2- ethylthio ethylmethanethiolsulfonate, 2-(phenoxy)ethyl benzenethiolsulfonate,2-phenylallyl methanethiolsulfonate, 2,2'-bis(phenylsulfonylthio)diethylsulfide and methylthiomethyl methanethiolsulfonate.

Representative aminocarbodithioate salts useful in the process of thisinvention include sodium, potassium, lithium and ammoniumdithiocarbamate, dimethylaminecarbodithioate,diethylaminecarbodithioate, l-piperidinecarbodithioate, and4-morpholinecarbodithioate.

The novel compounds of this invention are particularly useful aspesticides for the control of various fungal and bacterial organisms andother pests such as Bacillus subtilis, Staphylococcus aureus,Escherichia coli, Candida albicann, Trichophyton mentagrophytes,Venturia inaequalis, Piricutaria oryzae, Aerobacter aerogenes,Salmonella typ'hosa, Candidat pelliculosa, Pullularia lpullu- Ians,Rhizopus nigricans, Aspergillus terreus, Er'mtaria necatrix, Eimeriatenella and Daphnia.

The following examples describe completely representative specificembodiments and the best modes contemplated by the inventors of carryingout their invention. Temperatures given are centig ade,

4 EXAMPLE 1 'o-Nitrophenyl diethylaminecarbotrithioate o-Nitrophenylbenzenethiolsulfonate (14.8 grams; 0.0500 mole) in 75 milliliters ofmethylene chloride and 8.7 grams (0.0510 mole) of sodiumdiethylaminecarbodithioate in 75 milliliters of water were combined andstirred vigorously for 18 hours at room temperature. The organic layerwas separated, washed with water until free of water-soluble salts anddried over anhydrous magnesium sulfate. The solvent was removed byevaporation in vacuo, and the yellow, oily residue was crystallized(Norit) from 1:1 volumetric proportions of methylcyclohexane'and benzeneto give golden platelets, melting point 92-93. Recrystallization fromthe same methylcyclohexane-benzene mixture gave the pure o-nitrophenyldiethylaminocarbotrithioate, melting point 92.5-93".

Analysis.-Calcd. for C H N O S (percent): C, 43.68; H, 4.67; N, 9.27; S,31.80. Found (percent) :v C, 43.69; H, 4.64; N, 8.93; S, 32.07.

EXAMPLE 2 2,3,3-tribromoallyl 1-piperidinecarbotrithioate Sodiuml-piperidinecarbodithioate (6.7 grams; 0.033 mole) was added to asuspension of 15.0 grams (0.0330 mole) of 2,3,3-tribromoallylp-toluenethiolsulfonate in 250 milliliters of methanol with stirring atroom temperature. Dissolution of the reactants occurred immediately withconcomitant formation of a yellow-orange color. The mixture was stirredvigorously at room temperature for 1.75 hours, and the product,2,3,3-tribromoallyl l-piperidinecarbotrithioate, was obtained as a lighttan solid, melting point 84-86. Two recrystallizations from ethanol gavethe pure substance as white crystals, melting point 84.5- 865 iAnalysis.-Ca1cd. for C9H12BI'3NS3 (percent): C, 23.0; H, 2.57; Br, 51.0.Found (percent): C, 23.0; H, 2.57; Br,

BnC==CBrCHzSSCN b Sodium 4-morpholinecarbodithioate (18.5 grams; 0.100mole) was added in one portion to a solution of 45.1 grams (0.100 mole)of 2,3,3-tribromoallyl benzenethiolsulfonate in 750 milliliters ofmethanol at room temperature with vigorous stirring. Stirring wascontinued for 20 minutes, and the cream-colored precipitate which hadformed was collected on a filter, dried in vacuo and recrystallized fromethanol to give orange-brown crystals, melting point 112-1135". A secondrecrystallization from ethanol gave the pure 2,3,3-tribromoallyl4-morpholinecarbotrithioate as tan crystals, melting point 112.5-114.

Analysis.-Calcd. for C H Br NOS (percent): C, 20.4; H, 2.14; Br, 50.8.Found (percent): C, 20.4; H, 2.37; Br,50.7. Y

EXAMPLE 4 Pentaniethylene bis(4-morpholinecarbotrithioate) 6 v Nosswnmssciv b A solution of 3.7 grams (0.020 mole) of sodium 4-morpholinecarbodithioate in 25 milliliters of ethanol was added to asuspension of 2.9 grams (0.010 mole) of Allyll-piperidinecarbotrithioate S l CHFCHCHzSSbN A mixture of 16.5 grams(0.0726 mole) of allyl ptoluenethiolsulfonate and 13.3 grams (0.0726mole) of sodium 1-piperidinecarbodithioate in 200 milliliters of ethanolwas heated at reflux temperature for one hour. The solvent was removedby evaporation in vacuo, leaving a mixture of crystalline material andoil. The mixture was slurried in ether and filtered to remove theinsoluble byproduct, sodium p-toluenesulfinate. The ether was removed byevaporation in vacuo to give the crude product as an amber oil. Thematerial was chromatographed on an acid-washed activated alumina column,using 1:1 benzenepetroleum ether (boiling point 60-70"). The pure allyl1-piperidinecarbotrithioate was obtained as a yellow oil, 11 1.6339.

Analysis.-Calcd. for C H NS (percent): C, 46.31; H, 6.48; N, 6.00; S,41.21. Found (percent): C, 46.2; H, 6.56; N, 5.92; S, 41.70.

EXAMPLE 6 o-Xylylene bis (4-morpl1olinecarb otrithio ate S CHISSHIN CxmssoN' o A mixture of 10.0 grams (0.0306 mole) of oz,a'-biS-(methylsulfonylthio)-o-xy1ene and 11.3 grams (0.0612 mole) of sodium4-morpholinecarbodithioate in 300 milliliters of ethanol was stirred atroom temperature for 30 minutes. The precipitate which formed wascollected by filtration and stirred with hot ethanol. Theethanol-insoluble crude product was collected on a filter, air-dried andrecrystallized from acetonitrile to give the pure 0- xylylenebis(4-morpholinecarbotrithioate) as ivory-colored crystals, meltingpoint 174-175.

Analysis.Calcd. for ClBHgQNQOZSB (percent): C, 43.87; H, 4.91; N, 5.69.Found (percent): C, 43.7; H, 4.70; N, 4.54.

EXAMPLE 7 Propargyl 4-morpho-linecarbotrithioate A mixture of 9.0 grams(0.040 mole) of propargyl ptoluenethiolsulfonate and 7.4 grams (0.040mole) of sodium 4-morpholinecarbodithioate in 300 milliliters of ethylether was stirred at room temperature for 17 hours. During this periodof time the by-product sodium p-toluenesulfinate had precipitated aswhite crystals and was removed by filtration. The solvent was removedfrom the filtrate by evaporation in vacuo, leaving an oily, red solid.The substance was dissolved in a minimum amount of benzene andprecipitated by the addition of petroleum ether (boiling point 60-70) togive a yellow, crystalline,

crude product. Recrystallization from isopropanol gave the purepropargyl 4-morpholinecarbotrithioate as pale yellow crystals, meltingpoint 77-78.

Analysis.-Calcd. for C H N'OS (percent): C, 41.2; H, 4.75; N, 6.00.Found (percent): C, 41.4; H, 5.12; N, 6.11.

EXAMPLE 8 Methyl diethylamine earbotrithioate ems s oNwim),

A mixture of 41.0 grams (0.325 mole) of methyl methanetbiolsulfonate,116.8 grams (0.0682 mole) of sodium diethylaminecarbodithioate, 400milliliters of methylene chloride and 25 milliliters of water wasstirred vigorously at room temperature for 48 hours. The methylenechloride layer was separated, washed with water and dried over anhydrousmagnesium sulfate. Removal of the solvent by evaporation in vacuo gavethe methyl diethylaminacarbotrithioate as a yellow oil, 11 1.6111. Theoil was crystallized at low temperature from a solution of ethyl etherand petroleum ether (boiling point 60 70) to give a low melting yellowsolid, which was quickly collected on a sintered glass Buechner funneland dried in vacuo as a liquid in an Abderhalden drying pistol. Thepurified product, methyl diethylaminocarbotrithioate, was obtained as ayellow oil, 11 1.6118.

Analysis.Calcd. for C H NS (percent): C, 36.9; H, 6.71; S, 49.23. Found(percent): C, 37.5; H, 6.91; S, 49.57.

EXAMPLE 9 o-Nitrophenyl 4-morpholinecarbotrithioate N0: Q8 S C--'N 2) gV A solution of 16.0 grams (0.0865 mole) of sodium4-morpholinecarbodithioate in 50 milliliters of 'water was added to asolution of 25.1 grams (0.0850 mole) of o-ni' trophenylbenzenethiolsulfonate in 250 milliliters of methylene chloride, and thereaction mixture was stirred vigorously at room temperature for fourhours. After standing at room temperature for an additional 13 hours,the methylene chloride layer was separated, washed with water and driedover anhydrous magnesium sulfate. The solvent was then removed byevaporation in vacuo, leaving the crude product as bright yellowcrystals. Two recrystallizations from ethanol gave the pureo-nitrophenyl-4-morpholinecarbotrithioate as yellow crystals, meltingpoint 15 8-160.

Analysis.-Calcd. for C H N O S (percent): C, 41.75; H, 3.82; N, 8.86.Found (percent): C, 41.7; H, 3.87; N, 8.68.

EXAMPLE 10 o-Nitrophenyl 1-piperidinecarbotrithioate N O a A solution of20.1 grams (0.110 mole) of sodium l-piperidinecarbodithioate in 50milliliters of water was added to a solution of 29.5 grams (0.100 mole)of o-nitrophenyl benzenethiolsulfonate in 200 milliliters of methylenechloride, and the reaction mixture was stirred at room temperature for30 hours. The methylene chloride layer was separated, washed with waterand dried over anhydrous magnesium sulfate. The solvent was removed byevaporation in vacuo, leaving the bright yellow, crystalline, crudeproduct. Two recrystallizations from acetonitrile gave the pureo-nitrophenyl l-piperidinecarbotrithioate as bright yellow crystals,melting point 149.5- 151.5

7 Analysis.-Ca1cd. for C C N O S (percent): C, 45.84; H, 4.49; N, 8.91.Found (percent): C, 45.8; H, 4.51; N, 8.84.

EXAMPLE 11 2-methylbenzyl dimethylaminecarbotrithioate A mixture of 27.8grams (0.100 mole) of Z-methylbenzyl benzenethiolsulfonate and 19.7grams (0.110 mole) of sodium dimethylaminecarbodithioate dihydrate in300 milliliters of methanol was stirred at room temperature for hours.The white solid which had formed was collected on a filter and dried.The crude substance was twice recrystallized from ethanol to give thepure 2-methylbenzyl dimethylaminecarbotrithioate as colorless crystals,melting point 83-85 Analysis.-'Calcd. for C H NS (percent): C, 51.32; H,5.87; N, 5.44. Found (percent): C, 51.3; H, 6.01; N, 5.33.

EXAMPLE 12 Ethyl dimethylaminecarbotrithioate C H S S fiNUJHJ)! Amixture of 18.0 grams (0.0832 mole) of ethyl p-toluenethiolsulfonate and16.4 grams (0.0915 mole) of sodium dimethylaminocarbodithioate dihydratein 250 milliliters of methanol was stirred at room temperature for twohours. The solvent was then removed by evaporation in vacuo, leaving anoily residue which was slurried in ether and filtered to remove theinsoluble by-product, sodium p-toluenesulfinate. The ether filtrate wasdried over anhydrous magnesium sulfate and evaporated to dryness,leaving the crude product as a pale green oil. Treatment of a solutionof the crude product in methylene chloride with activated alumina, withsubsequent filtration and evaporation of the solvent, gave the ethyldimethylaminecarbotrithioate as a pale yellow oil, n 1.6205. (Lit. n1.6278; A. A. Watson, J. Chem. Soc., 1964, 2100).

EXAMPLE 13 n-Dodecyl dimethylaminecarbotrithioate CHa(CH2)nS S fiNKJHg);

A solution of 13.8 grams (0.0772 mole) of sodiumdimethylaminecarbodithioate dihydrate in 150 milliliters of methanol wasslowly added with stirring to a suspension of 25.0 grams (0.0702 mole)of n-dodecyl p-toluenethiolsulfonate in 150 milliliters of methanol. Thereaction mixture was stirred at room temperature for 16 hours duringwhich time the product precipitated. The white, crystalline precipitatewas collected on a filter and recrystallized from ethanol to give thepure n-dodecyl dimethylaminecarbotrithioate as colorless crystals,melting point 48-50".

Analysis.-Calcd. for C H NS (percent): C, 56.02; H, 9.72; N, 4.36. Found(percent): C, 56.3; H, 9.98; N, 4.37.

EXAMPLE 14 Benzyl dimethylaminecarbotrithioate Q-omssomcmn A solution of17.8 grams (0.0640 mole) of benzyl ptoluenethiolsulfonate in 150milliliters of methanol was added to a stirred suspension of 12.6 grams(0.0700 mole) of sodium dimethylaminecarbodithioate dihydrate in 150milliliters of methanol, and the mixture was stirred at room temperaturefor 18 hours. During the reaction period the crude product precipitatedas white crystals and Z-methylbenzyl 1-piperidinecarbotrithioate Asolution of 24.1 grams (0.110 mole) of sodium 1-piperidinecarbodithioate in 200 milliliters of methanol was added withstirring to a suspension of 27.8 grams (0.100 mole) of Z-methylbenzylbenzenethiolsulfonate in milliliters of methanol. The formation of awhite precipitate was observed immediately. The reaction mixture wasallowed to stand at room temperature for 20 hours and was then filteredto collect the white, crystalline, crude product. Recrystallization fromisopropanol gave the pure 2-methylbenzyl 1-piperidinecarbotrithioate ascolorless crystals, melting point 103-105 AnaIysis.-Calcd. for C H NS(percent): C, 56.56; H, 6.44; N, 4.71. Found (percent): C, 56.6; H,6.55; N, 4.87.

EXAMPLE 16 2- (methylthio ethyl dimethylaminecarbotrithioate CHaSCHzCHzSSfiN(CH.-4)2

A solution of 16.1 grams (0.0431 mole) of Z-(methylthio)ethylp-iodobenzenethiolsulfonate in 75 milliliters of methanol was added withstirring to a solution of 8.5 grams (0.047 mole) of sodiumdimethylaminecarbodithioate dihydrate in 75 milliliters of methanol, andthe reaction mixture was stirred for 15 hours at room temperature. Thesolvent was removed by evaporation in vacuo, leaving a residue of whitesolid. The residue was extracted with methylene chloride and the sodiump-iodobenzenesulfinate by-product removed by filtration. The filtratewas concentrated to give the crude product as a white solid, which wascollected on a filter and recrystallized from methanol to give the pureZ-(methylthio) ethyl dimethylaminecarbotrithioate as colorless needles,melting point 36-37 Analysis.-Calcd. for C H NS (percent): C, 31.68; H,5.76; N, 6.16. Found (percent): C, 31.7; H, 6.00; N, 5.93.

EXAMPLE 17 2- (methylthio) ethyl dimethylaminecarbotrithioate A solutionof 10.6 grams (0.0592 mole) of sodium dimethylaminecarbodithioatedihydrate in 100 milliliters of methanol was purged of air by a streamof nitrogen. 2-(methylthio)ethyl methanethiolsulfonate (10.0 grams,0.0537 rnole) in 100 milliliters of methanol was then added slowly withstirring at room temperature. After the mixture had been stirred undernitrogen at room temperature overnight the solvent was removed byevaporation in vacuo to leave an oily residue which, when shaken withmethylene chloride, left a water miscible layer which was separated fromthe organic phase and discarded. The methylene chloride solution wasconcentrated to give white crystals, melting point 35-36", with someremain- EXAMPLE 18 2-(methylthio)ethyl 4-morpholinecarbotrithioateCHISCHZCHISSCN b A solution of 21.8 grams (0.118 mole) of sodium 4-morpholinecarbodithioate in 150 milliliters of methanol was added slowlyat room temperature to a stirred solution of 20.0 grams (0.107 mole) of2-(methylthio)ethyl methanethiolsulfonate in 150 milliliters ofmethanol. Stirring was continued for 15 hours, and the solvent was thenremoved by evaporation in vacuo. The yellow oily residue was shaken withwater and the mixture extracted with methylene chloride. After theextract was dried over anhydrous magnesium sulfate the methylenechloride was removed by evaporation, leaving 27.0 grams of a turbid,yellow oil 11 1.6473. Residual solvent was removed by vacuumdistillation, leaving 25.0 grams of yellow oil which was dissolved inmethylene chloride, the solution treated with activated charcoal andfiltered. Upon removing the methylene chloride in vacuo, the residue wasfound to consist of a clear, yellow oil, ri 1.6445.

Analysis.Calcd. for C H NOS (percent): C, 35.66; H, 5.61; N, 5.20. Found(percent): C, 35.4; H, 5.48; N, 5.43.

EXAMPLE 19 n-Dodecyl 1-piperidinecarbotrithioate A solution of 9.7 grams(0.0440 mole) of sodium 1- piperidinecarbodithioate in 150 millilitersof methanol was added with stirring to a suspension of 14.3 grams(0.0401 mole) of n-dodecyl p-toluenethiolsulfonate in 150 milliliters ofmethanol at room temperature. A thick, white precipitate formed almostimmediately. The reaction mixture was allowed to stand at roomtemperature for 16.5 hours. The mixture was then collected on a filterand dried. Two recrystallizations from ethanol gave the pure product aswhite crystals, melting point 47.5-

Analysis.-Calcd. for C H NS (percent): C, 59.78; H, 9.75; N, 3.88. Found(percent): C, 59.8; H, 10.04; N, 4.14.

EXAMPLE 20 Thiodiethylene bis(4-morpholinecarbotrithioate NCSSCHzCHzSCHzCHzS SCN b t. it

Sodium 4-morpholinecarbodithioate (18.5 grams; 0.100 mole) was added toa warm, stirred solution of 21.7 grams (0.0500 mole) of2,2-bis(phenylsulfonylthio)diethyl sulfide with the immediate formationof a voluminous, white precipitate. The reaction mixture was heatedunder reflux with stirring for 15 minutes and the white, crystallineproduct collected on a filter and washed with water to remove the sodiumbenzenesulfinate by-product. The crude product was recrystallized frommethanol to give a very pale yellow solid, melting point l16.5-117.5. Asecond recrystallization from methanol gave a pure product as paleyellow crystals, melting point 117-117.5.

Analysis.-Calcd. for C I-1 18 0 8 (percent): C, 35.27; H, 5.07; N, 5.88.Found (percent): C, 35.2; H, 4.97; N, 5.79.

10 EXAMPLE 21 2 methylthio ethyl diethylaminecarbotrithioate CHaS011201125 5 g mme:

To a stirred solution of 27.2 grams (0.121 mole) of sodiumdiethylaminecarbodithioate trihydrate in milliliters of methanol wasslowly added a solution of 15.0 grams (0.0806 mole) of2-(methylthio)ethyl methanethiolsulfonate in 100 milliliters of methanolunder nitrogen. The reaction mixture was then stirred at roomtemperature under nitrogen for 18 hours. Evaporation of the solvent leftan oil which was washed with water. The water washings were combined andwashed with methylene chloride. The oil portion was added to themethylene chloride extract and the resulting solution dried overanhydrous magnesium sulfate. The solution was then treated withdecolorizing charcoal, filtered and concentrated in vacuo to give aclear, yellow oil, 11 1.6137.

Analysis.-Calcd. for C H NS (percent): C, 37.57; H, 6.71; N, 5.48. Found(percent): C, 38.0; N, 6.69; N, 5.40.

EXAMPLE 22 2- (ethylthio) ethyl 4-morpholinecarbotrithioate A mixture of11.0 grams (0.055 mole) of 2-(ethylthio)ethyl methanethiolsulfonate and12.2 grams (0.066 mole) of sodium 4-morpholinecarbodithioate in 300milliliters of methanol was stirred at room temperature for 18 hours.The solvent was removed in vacuo, leaving an oily, crystalline masswhich was stirred in ether and filtered to remove the insolublebyproduct. The filtrate was dried over anhydrous magnesium sulfate andwas evaporated to dryness to give a yellow oil. The oil was crystallizedby cooling in a. Dry-Ice-methylene chloride bath and recrystallized frommethanol. Two recrystallizations from isopropanol gave the puresubstance as colorless crystals, melting point 31-325.

Analysis.Calcd. for C H NOS, (percent): C, 38.13; H, 6.05; N, 4.95.Found (percent): C, 38.0; H, 5.85; N,

EXAMPLE 23 2-phenoxyethyl 4-morpholinecarbotrithioate @o-omcms s on 2)ll k A solution of 15.1 grams (0.0816 mole) of sodium 4-morpholinecarbodithioate in milliliters of methanol was added withstirring to a suspension of 20.0 grams (0.0680 mole) of 2-(phenoxy)ethyl benzenethiolsulfonate in 150 milliliters of methanol. Athick, white precipitate began forming immediately. The reaction mixturewas stirred at room temperature for 19 hours, and the precipitate wascollected on a filter. Recrystallization of product from methanol gavethe pure substance as colorless crystals, melting point 8991.

Analysis.-Calcd. for C 'I-I,',N0 S (percent): C, 49.49; H, 5.43; N,4.44. Found (percent): C, 49.2; H, 5.50; N, 4.47.

EXAMPLE 24 2-phenylallyl 4-morpholinecarbotrithioate A solution of 16.7grams (0.0732 mole) of Z-phenylallyl methanethiolsulfonate and 16.3grams (0.0878 mole) of sodium 4-morpholinecarbodithioate in 300milliliters of methanol was stirred at room temperature for 28 hours.The solvent was removed in vacuo, leaving a yellow residue which wasstirred in ether and filtered to remove the insoluble by-product, sodiummethanesulfinate. The ether filtrate was dried over anhydrous magnesiumsulfate and evaporated to dryness to obtain a yellow, viscous oil.Trituration with a small amount of cold ether gave the crude,crystalline product which was collected on a filter. Recrystallizationof product from ethanol gave the pure substance as colorless crystals,melting point 69.571.

Analysis.-Calcd. for C H NOS (percent): C, 53.98; H, 5.51; N, 4.50.Found (percent): C, 54.0; H, 5.38; N, 4.31.

EXAMPLE 25 Thiodiethyle'ne bis (dimethylaminecarbotrithioate) CH; H3

NC s s CHflCHiS CHICHlS 3 ON CH: g H C H:

Sodium dimethylaminecarbodithioate dihydrate (14.2 grams; 0.0792 mole)was added to a warm, stirred solution of 17.2 grams (0.0396 mole) of2,2-bis(phenylsulfonylthio)diethyl sulfide in 700 milliliters ofmethanol. The mixture was heated under reflux with stirring for onehour, after which time the methanol was removed by evaporation in vacuo.The solid residue was extracted with water at room temperature to removethe by-product, sodium benzenesulfinate, collected on a filter and driedin vacuo over calcium chloride. Two recrystallizations from ethylacetate gave the pure substance as colorless crystals, melting point105l05.5.

Analysis.Calcd. for C H N s (percent): C, 30.58; H, 5.13; N, 7.14. Found(percent): C, 30.6; H, .510; N, 7.25.

EXAMPLE 26 Methylthiomethyl 4-morpholinecarbotrithioate A solution of13.0 grams (0.0700 mole) of sodium 4- morpholinecarbodithioate in 125milliliters of methanol was added to a solution of 10.0 grams (0.0580mole) of methylthiomethyl methanethiolsulfonate in 125 milliliters ofmethanol, and the reaction mixture was stirred at room temperature for16 hours. The white precipitate, which had formed during the reactionperiod, was collected on a filter and recrystallized from methanol togive the pure methylthiomethyl 4-morpholinecarbotrithioate as paleyellow crystals, melting point 55-57".

Analysis.-Calcd. for C H NOS (percent): C, 32.88; H, 5.13; N, 5.49.Found (percent): C, 33.1; H, 4.81; N, 5.41.

The compounds of the present invention are variously useful aspesticides for the control of various bacteria, fungi, mollusks,crustaceans, insects and terrestial plants. For such use, the unmodifiedcompounds can be employed. Alternatively, the compounds can be dispersedon an inert finely divided solid and the resulting preparation employedas a dust. Also, such compounds or dust compositions containing saidcompounds can be dispersed in water with or Without the aid ofadditional wetting agents. and the resulting aqueous dispersionsemployed as sprays. In other procedurdes, the compounds can be employedas solutions in petroleum distillates or in other solvents or asconstituents of oil-in-water or water-in-oil emulsions. Such liquidcompositions can be employed as sprays, drenches or washes.

In representative operations, the compound of Example 2 gives goodcontrol of nymphal American cockroaches. In the test method, a papercylindrical cage is provided, fitted on the bottom with a number 52Whatman filter paper and on the top with a retaining screen. Twenty-fivenymphal cockroaches are inactivated with CO and immersed in an aqueousdispersion of 1,000 parts per million by Weight of the compound ofExample 2 contained in the cage. The water is drawn off by suctionthrough the filter paper. The nymphs are then fed with sugar water andleft in the cage for three days, when a mortality count is made. Undersuch conditions, substantially complete control is attained. The samecompound is separately dispersed in a series of melted nutrient agarsamples to product a bacteriological culture medium containing 500p.p.m. thereof by weight of ultimate medium. Each of these media is thenpoured into a separate Petri dish and allowed to solidify. Thesolidified agar surface in each Petri dish is separately inoculated withone of Staphylococcus aureus, Bacillus substilis, Aspergillas terreus,Candida pelliculosa, Pullalarza pullulans or Salmonella typhosa, theinoculation being carried out by mopping the agar surfaces with a swabfrom a 24-hour broth culture of the organism. After 72 hours incubationat 30 C., the agar surface of each Petri dish is examined formicroorganisms. In each of the series, the control is 100 percent. Acontrol culture, to which none of the compound is added, shows vigorousgrowth.

The compound of Example 3 is similarly 100 percent effective againstStaphylococcus aureus and Bacillus substilis at a concentration of 500p.p.m.

The compound of 'Example 5 is similarly effective against Staphylococcusaureus, Candida albicans and Trichophyton mentagrophytes, but at 100p.p.m. concentration. This compound is also effective in controllingDaphnia and Carassius auratus when 100 p.p.m. of compound is dispersedin water containing these organisms. Piricutaria oryzae is controlled100 percent by application of an aqueous dispersion containing 100p.p.m. of compound. Amaranthus species is 100 percent controlled byapplication to the soil of 10 lb./acre of the compound applied inaqueous dispersion as a drench to soil containing viable seed of saidspecies.

The compound of Example 7 is 100 percent effective against the Americancockroach at a concentration of 1000 p.p.m. used in the form of anaqueous dispersion. An aqueous dispersion of 150 p.p.m., when sprayed oncucumber plants and potato plants, respectively, gives 100 percentcontrol against Erysiphe cichoracearum and percent control againstPhytophthora infestans.

The compound of Example 24 is similarly percent effective against theAmerican cockroach and against Staphylococcus aureus at 500 p.p.m., and100 percent elfective against Candida albicans, Trichophytonmentagrophytcs, Bacillus subtilis, Aspergillus terreus, Candidapellucwlosa, Pullularia pullulans and Mycobacterium phlei, all at aconcentration of 100 p.p.m.

The following table shows effectiveness of other compounds at the statedconcentrations, using tests as described above.

13 14 TABLECnt11med What is claimed is:

c 1. A compound corresponding to the formula t ti Compound Eflective for100% control of-- its; R R NC(=S)SS(CH,),,SSC(=S)NR R Example 21 i C 'gl88 5 wherein n represents an integer from 1 to 12, inclusive, 1 5,523,100 and wherein R and R individually represent lowcralkyl {88 having 1to 4 carbon atoms or hydrogen and together 100 represent the remainingportion of a heterocyclic ring 100 100 selected from the groupconsisting of 4-morpho1ino and 1- piperidino moieties.

Example 22 23?, 2- The compound of claim 1 which is pentamethylene Tmentaprophyt 100 bis(4-morphol1necarbotrithioate). B aubtilw 100 A.terrcua. 100 C'Pemmlm" 100 References Cited P. pullulam 100 Breadmoldmflusfl- UNITED STATES PATENTS EMPM 3 248 400 4/1966 Flieg et al260-4246 B x n 5 i i fifiifiii'fiiflfff 533 3,644,408 '2/1972 Hill260-446 B Bean mildew 100 Emnpla gmg {8g DONALD G. DAUS, PrimaryExaminer :1';; ;11;: 1331;133: 33; g I. H. 'I URNIPSEED, AssistantExaminer Example 4 Amuranthus supp l US. Cl. X.R.

Example25 5 LbJacre.

